Diamine containing softener compositions

ABSTRACT

The color and odor of technical N-alkyl (C12-C22)-1, 3-propylene diamines may be improved by treating the diamine with acrylic acid and/or methacrylic acid monomer, after which the monomer is polymerized and neutralized. The addition of small amounts of urea and/or sugar to the treated N-alkyl-1, 3-propylene diamine further improves the fabric softening properties of the diamines and reduces fabric discoloration.

United States Patent Renold DIAMINE CONTAINING SOFTENER COMPOSITIONSAdolph Renold, Somerset. NJ.

Colgate-Palmolive Company. New York N.Y.

Filed: Oct. 25, 1972 Appl. No.: 300,580

Inventor:

Assignee:

US. Cl. 252/88; 260/78 SC Int. Cl D06m 1/14 Field of Search 252/8.8;260/78 SC Apr. 22, 1975 3.632.420 l/l972 Kuhn 252/8.8 X

Primary E.\'uminerStephen .l. Lechert, Jr. Anurney. Agent or FirmHerbertS. Sylvester;

Murray M. Grill; Norman Blumenkopf [57] ABSTRACT The color and odor oftechnical N-alkyl (C -C )-l. 3-propylene diamines may be improved bytreating the diamine with acrylic acid and/or methacrylic acid monomer,after which the monomer is polymerized and neutralized. The addition ofsmall amounts of urea and/or sugar to the treated N-alkyl-l, 3-propylene diamine further improves the fabric softening properties ofthe diamines and reduces fabric discoloration.

4 Claims, N0 Drawings DIAMINE CONTAINING SOFTENlER COMPOSITIONSBACKGROUND OF THE INVENTION This invention relates to methods forimproving the color. odor. and fabric softening properties of N-higheralkyl-l. 3-propylene diamines. and of fabric softening compositionsincorporating the improved N-higher alkyl propylene diamines.

The use of synthetic detergent compositions in heavy-duty householdlaundering has become a widespread practice. The formulationsconventionally employed generally comprise synthetic detergentsurfactants and alkaline builder salts which function to enhance thecleaning levels of synthetic materials. Some inorganic builder materialspresent in detergent formulations have been known to have a tendency toreact with the metal ions present in the washing solution. precipitating out insoluble salts which deposit on the textile materialbeing laundered. Such deposited mineral salts give the launderedfabrics, a poor. boardy feel particularly at those areas of the fabricwhich are exposed to frictional and creasing effects such as collars andcuffs. This poor hand oflaundered fabrics and resulting discomfortduring use have in part resulted in the creation of a large andexpanding market for softener formulations capable of improving thesoftness or hand" of laundered textiles. It has been found that thetreatment of such materials with softening agents improves theirsoftness of feel and may prolong the useful life of the textilematerials. In addition. it has been found that such treatment generallyresults in a fabric having a reduced tendency to accumulate electricalcharges. which fact facilitates the ironing of treated materials.

N-higher alkyl-l. 3propylene diamines are well known softening agentsand are compatible with most synthetic detergent formulations. However.heretofore they have not won much acceptance for use as fabricsofteners. because the generally available technical grade N-higheralkyl- 1 3-propylene diamines are characterized by an unpleasant odorwhich cannot be masked by the detergent perfumes currently available.

Additionally, the technical grade N-higher alkyl-l. 3-propylene diamineshave a tendency to discolor synthetic fabrics such as polyamides.polyesters. and the like, in regular household laundry; thisdiscoloration darkens upon aging. The best explanation for thediscoloration is that it is a heavy metal (e.g. iron) catalyzeddecomposition of the diamine. which is a known heavy metal scavenger andused as such in the oil industry.

Presently, one of the best known methods for improving the properties oftechnical grade N-higher alkyl propylene diamines is by vacuumdistillation. However. this method is expensive and relativelyineffective: the resulting diamine is not improved signifr cantly. andit is prohibitively expensive for use in detergent formulations. Intergitometer tests using a commercially available laundry detergent. nosignificant difference between the crude and the distilled diamine wasfound. Nylon cleaning was particularly poor.

SUMMARY OF THE INVENTION It has now been discovered that the propertiesof technical grade N-higher alkyl-l. 3-propylene diamines, where thealkyl group contains from 12 to 22 carbon atoms. may be significantlyimproved by treatment with acrylic acid monomer. methacrylic acidmonomer. or mixtures of both. and then polymerizing and neutralizing themonomer.

Various methods for preparing the N-higher alkyl-l 3-propylene diaminesto be treated are known. One method consists in reacting a fatty amine(e.g.. tallow amine or hydrogenated tallow amine) with acrylonitrile andthen hydrogenating the reaction product. as shown in the followingequations:

The resulting diamines have an unattractive color and a malodorcharacteristic of amines. This color and amine malodor can be reduced.however. by treating the technical diamine with acrylic acid and/ormethacrylic acid monomer. polymerizing the monomer. and neutralizing theresulting polymer. The monomer acts as an acidic scavenger byinteracting with colorforming impurities. and the alkali polyacrylate.prepared in situ. reduces the heavy metal sensitivity ofdiamine-containing surfactants.

The ratio of N-higher alkyl-l 3-propylene diamine to acrylic acid ormethacrylic acid monomer ranges from about 30:1 to about 5:1 by weight.

The addition of small amounts of urea or sugar or mixtures of urea andsugar to the treated Nalkyll 3- propylene diamines greatly andunexpectedly improves the softening properties of the diamines. The ureaand- /or sugar is present in amounts ranging from about I percent toabout 200 percent by weight of the treated diamine.

The N-higher alkyl-l. 3-propylene diamines treated according to thepresent invention are valuable softening agents for textiles and fabricsmanufactured from synthetic and natural fibers and blends thereof.inclusive of cellulose. Dacron-cotton blends. nylon. wool. cotton.Orlon. Orlon blends. and the like. The treated diamines may be used as arinse additive or in conjunction with a suitable laundry detergent inthe wash cycle. Where urea and/or sugar are added to the diamine. theresulting mixture can be used in the same manner.

Where the treated N-higher alkyl-l. 3-propylene diamines of the presentinvention are to be used as rinse additives. they may be mixed withcompatible solid additives and fillers. such as aluminum silicate.sodium tripolyphosphate. sodium carbonate, sodium sulfate. and the like.The concentration of the treated N-higher alkyl- 1 3-propylene diaminein these compositions can range from about 5 percent to about percent.although a range of between 15 percent and 30 percent is preferred.

Additionally. the treated N-higher alkyl-l. 3- propylene diamines may bedispersed or dissolved in suitable liquid systems where a liquid rinseadditive is desired. Examples of such liquids include propylene glycol.ethylene glycol. and isopropanol'. the diamine may then be present inamounts ranging from 10% to 95 percent of the total weight of the finalformulation. although a range of from about 30 percent to about percentis preferred.

The N-higher alkyl-l. 3-propylene diamines treated according to thepresent invention are particularly well suited for incorporation indetergent formulations. In such detergent formulations the treateddiamine comprises from about 1 percent to about percent by weight of thetotal composition. and preferably from about 5 percent to about 50percent by weight of the total composition.

The detergents containing the treated diamines of this invention cancontain any of the usual compatible adjuvants diluents. and additives.including other detergents. for example. anionic. nonionic. oramphoteric synthetic detergents: perfumes. antiredeposition agents.bacteriostatic agents. dyes. fluorescers. brighteners. suds builders.suds depressors. and the like without detracting from the advantageousproperties of the composition.

The treated N-higher alkyl-l. 3-propylene diamines of the presentinvention impart the desired degree of softness to textiles treatedtherewith when utilized in amounts of from about 0.05 percent to about 5percent. and. preferably. in amounts ranging from about 1 percent toabout 3 percent by weight of the fabric.

As examples of suitable synthetic anionic detergents there may be cited.for example, the sodium salts of higher alkyl mononuclear aromaticsulfonates such as tl'ie higher alkyl benzene sulfonates containing fromto 16 carbon atoms in the alkyl group in a straight or branched chain;the higher alkyl toluene. xylene. and phenol sulfonates; alkylnaphthalene sulfonate. ammonium diamyl naphthalene sulfonate. and sodiumdinonyl naphthalene sulfonate.

Other anionic detergents are the olefin sulfonates. including long-chainalkene sulfonates. long-chain hydroxy alkane sulfonates or mixtures ofalkanesulfonates and hydroxyalkanesulfonates. These olefin sulfonatedetergents may be prepared. in known manner. by the reaction of 50;;with long chain olefins (of 8-25. preferably 12-21. carbon atoms) of theformula R'CH=CHR". where R is alkyl and R" is alkyl or hydrogen. toproduce a mixture of sultones and alkenesulfonic acids. which mixture isthen treated to convert the sultones to sulfonates. Examples of othersulfate or sulfonate detergents are primary paraffin sulfonates of aboutl0-20. preferably about 15-20. carbon atoms; sulfates of higheralcohols; salts of alphasulfofatty esters (e.g.. of about l0-20 carbonatoms. such as methylalpha-sulfomyristate or alpha-sulfotallowate).

Examples of sulfates of higher alcohols are sodium lauryl sulfate.sodium tallow alcohol sulfate. Turkey Red Oil or other sulfated oils. orsulfates of monoor di-glycerides of fatty acids (e.g.. stearicmonoglyceride monosulfate alkyl poly (ethenoxy) ether sulfates such asthe sulfates of the condensation products of ethylene oxide and laurylalcohol (usually having one to five ethenoxy groups per molecule);lauryl or other higher alkyl glyceryl ether sulfonates; aromatic poly(ethenoxy) ether sulfates such as the sulfates of the condensationproducts of ethylene oxide and nonyl phenol (usually having one to sixoxyethylene groups per molecule).

Nonionic surface active agents include those surface active or detergentcompounds which contain an organic hydrophobic group and a hydrophilicgroup which is a reaction product of solubilizing groups such ascarboxylate or hydroxyl. with ethylene oxide or with the polyhydrationproduct thereof. polyethylene glycol.

As examples of nonionic surface active agents which may be used theremay be noted the condensation products of alkyl phenols with ethyleneoxide. e.g.. the reaction product of isooctyl phenol with about six toethylene oxide units; condensation products of alkyl thiophenols with 10to 15 ethylene oxide units; condensation products of higher fattyalcohols such as tridecyl alcohol with ethylene oxide; ethylene oxideaddends of monoeste'rs of hexahydric alcohols and inner esters thereof.such as sorbitan monolaurate. sorbitol monooleate and mannitolmonopalmitate. and the condensation products of polypropylene glycolwith ethylene oxide. Other nonionics include amine oxides. e.g.. lauryldimethyl amine oxide; sulfoxides and the like.

In addition to the treated N-higher alkyl-l 3- propylene diamines andactive detergent. detergent formulations prepared according to thepresent invention may contain one or more water-soluble detergencybuilder salts. either of the organic or the inorganic type. andpreferably alkaline salts.

Examples of water-soluble inorganic detergency builder salts are alkalimetal carbonates. phosphates. polyphosphates. sulfates. silicates, etc.Specific examples of such salts are sodium potassium. and lithiumtripolyphosphates. carbonates. pyrophosphates. orthophosphates. andhexametaphosphates; sodium. potassium. and lithium sulfates; and sodiumpotassium. and lithium silicates. Examples of organic alkalinedetergency builder salts are l) alkali metal aminopolycarboxylates[e.g.. sodium and potassium ethylenediamine tetraacetates. N-(2-hydroxyethyl) nitrilo diacetates];

(2) alkali metal salts of phytic acid (e.g.. sodium and potassiumphytates see U.S. Pat. No. 2.739.942); (3) water-soluble salts ofethane-l-hydroxy-l. ldiphosphonate (e.g.. the trisodium and tripotassiumsalts see U.S. Pat. No. 3.159.58l (4) water'soluble salts ofpolycarboxylate polymers and copolymers (e.g.. homopolymers of itaconicacid. aconitic acid. maleic acid. mesaconic acid. fumaric acid. andmethylene malonic acid. and copolymers thereof with other compatiblecopolymerizable monomers such as ethylene); and mixtures thereof.

Because of the added detergent needed to counterbalance the treatedN-higher alkyl-l. 3-propylene diamine softener and because softenerstend to be oily materials. the detergents incorporating the diaminestreated according to the present invention have a tendency to be lazy.i.e.. they do not flow easily. It was observed that the addition of ureaand/or sugar to the treated diamine reduces the oiliness of thesoftener. Both urea and sugar display softening properties when combinedwith the diamine. and. additionally, they absorb diamine. Optimumamounts of both. together with the conventional amounts of an anticakingagent such as heat'treated aluminum silicate. yield a detergent withvery desirable flow properties.

The detergents of the present invention may be formulated as liquids.solids. pastes. gels. etc. The detergents of the present invention canbe effectively used for laundering fabrics in water having a temperaturefrom about 60 to about 2 l 2F.. the detergents containing the treatedN-higher alkyl-l. 3-propylene diamines exhibiting unusually effectivedetergency and fabric softening characteristics in both cold and hotwater. The detergent composition concentration in the wash water shouldrange from about 0.05 percent to about 0.5 percent by total weight.

In washing fabrics. the addition of the fabrics and the detergentcomposition can be conducted in any suitable conventional manner. Thus.for example. the fab rics can be added to the container or washer eitherbefore or after the washing solution is added. The fabrics are thenagitated in the detergent solution for varied periods of time. a washcycle of from 5 to 15 minutes being generally used in the washing cycleof an automatic agitator type washer. After the fabrics are rinsed. theyare dried first by spinning and then by contact with air as in aconventional hanging of the fabrics on a clothesline or in an automaticdryer type system.

In the preparation of the detergent compositions of the presentinvention. generally, the organic detergent and the treated N-higheralkyl-l. 3-propylene diamine. the urea and/r sugar. if it is used. aswell as the builders and any minor ingredients are incorporated into thecomposition prior to its conversion into the final form. e.g,. detergentgranules. flakes. bar. etc. However. the individual components of thedetergent of the present invention can be added in the form of particlesor directly as a liquid to produce a liquid detergent composition.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The following specific examplesillustrate various embodiments of the present invention. It is to beunderstood. however, that such examples are presented for the purposesof illustration only, and the present invention is in no way to bedeemed as limited thereby.

EXAMPLE I Seven hundred twenty grams of technical grade N- tallow l.3-propylene diamine was placed into a hooded tank equipped with steamcoils and a stirrer. The diamine was heated to 95C.. and purged withnitrogen for one hour to remove and modify any potentially color causingimpurities prior to the polymerization reaction. The temperature of thediamine was kept around 95C., and 0.25 gram mercaptosuccinic acid and 30grams of methacrylic acid were added. The mixture was stirred undernitrogen for 1 hour. One gram of VAZO (duPont azobisisobutyronitrilecatalyst) was added to the mixture. The nitrogen was discontinued. andthe mixture was heated slowly. Forty minutes later the temperature ofthe reaction mixture was 117C., and another 1.0 gram of VAZO was added.Stirring with heat was continued for an hour. Then 18.2 grams of sodiumcarbonate was added to neutralize the polyacrylic acid; the mixture waskept at about 1 17C. for an hour with stirring to complete theneutralization.

The diamine treated as described above was a superior fabric softenerbecause of its reduced tendency to pick up color by combining with heavymetals and traces of tannin-like materials present in tap water.

EXAMPLE II A phosphate-based softener formulation for use either in thewash cycle or the rinse cycle is prepared from the diamine treatedaccording to Example 1. One hundred fifty grams of the softener ofExample I was heated to 98C. and 28 grams of sugar was added with goodstirring. After 5 minutes 115 grams of urea was added with goodstirring. The temperature of the mixture was maintained at about 98C.for 20 minutes more.

The mixture above was added to 600 grams lowdensity sodium phosphate ina Hobart mixer and stirred for twenty minutes. The homogeneous mixturewas passed through :1 mesh sieve and was ready for use.

EXAMPLE III A solid fabric softener composition for use in either thewash cycle or the rinse cycle was prepared from the softener of ExampleI. Five hundred ten grams of technical sodium tripolyphosphate and 2grams of sodium carbonate were mixed for five minutes. One hundred twograms of the softener of Example I (molten) was added and thecombination was mixed for 20 minutes in a Hobart mixer at roomtemperature. Then 76 grams of urea (8 mesh) and 25 grams of sugar wereadded. and the total was mixed for 40 minutes in a Hobart mixer at roomtemperature. Finally, 15 grams of heattreated aluminum silicateanticaking agent was added, and the combination was mixed for fifteenminutes in a Hobart mixer at room temperature. The resulting fabricsoftener composition was granular and free flowing.

EXAMPLE IV A rinse additive was formulated from the followingingredients:

Softener of Example I 20 grams Urea 6 grams Synthetic detergent 18%anionic/ 7% sodium silicate/339i sodium phosphate/(L4G C MC 30 gramsTechnical sodium tripolyphosphate 54 grams Heat-treated aluminumsilicate 30 grams Optical brightener 0.4 gram Perfume 0.4 ml.

The resulting fabric softener rinse additive had excellent solubilityunder use conditions and exhibited marginal dusting.

EXAMPLE V The following ingredients were heated in a mortar to 4852C..powdered, cooled to room temperature. passed through an 8 mesh sieve,and ball milled for 2 hours:

Softener of Example I 21 grams Sodium carbonate 2] grams Urea 12 gramsHeat-treated aluminum silicate 32 grams Carhoxymethylcellulose 12 gramsOptical brightener 0.4 grams Perfume 0.4 ml.

The resulting rinse additive formulation exhibited good solubility underuse conditions and left very little dust on fabrics treated therewith.

EXAMPLE VI A detergent composition was prepared based on the fabricsoftener of Example V as follows:

Softener of Example 164 grams Synthetic detergent (109i anionic/27:

nonionic/l lr nonionic/339i sodium tripolyphosphate/ISI: sodium silcate638 grams Perfume 1.2 ml. Optical brighteners 7.2 grams EXAMPLE VII Aliquid fabric softener composition was formulated from the followingingredients:

Softener of Example I 57 grams Ethylene glycol 25 grams L'rea 3 gramsSugar 2 grams EXAMPLE VIII The following ingredients were placed into amortar:

Softener of Example I 34 grams Sodium carbonate 23 grams Urea l2 gramsHeat-treated aluminum silicate grams Carboxymethylcellulose 4 gramsSynthetic detergent I071 anionic/29? nonionicll l nonionic/33'/1 sodiumtripolyphosphate/7.5 2 sodium silicate) 46 grams The ingredients wereplaced into a l 10C. oven until warmed to a temperature of 5055C. Themixture was stirred lightly and cooled to room temperature by placingthe powder into the freezing compartment of a refrigerator for 45minutes. The cooled mixture was then passed through a 12 mesh screen.The resulting mixture was uniform and ready for further dilution to adetergent formulation.

The mixture was used to prepare a detergent composition as follows:

Mixture of softener 87.0 grams Synthetic detergent( [O /l anionic/ 29;nonionic/l'l: nonionicl33 /r sodium tripolyphospate/TSV: sodiumsilicate) 3|} grams Optical brighteners 8 grams Perfume 2.0 ml.

EXAMPLE IX The softeners of the present invention are particularlysuitable for use in phosphate-free detergents. A concentrated softenerbase was formulated as follows:

Softener of Example I 34 grams Sodium carbonate 23 grams Urea 12 gramsHeat-treated aluminum silicate 23 grams C arboxymethylcellulose 4 gramsLow foam synthetic detergent linear dodccyl benzene sulfonate/ 257:silicate/471 ethoxylated fatty alcohol/271 (MC/6V1 soap) 46 gramsSoftener mixture 87 grams C arboxymethylcellulosc 4 grams Low foamsynthetic detergent (25% linear dodecyl benzene sulfonate/lfi /rsilicate/471 ethoxylated fatty alcohol/ 27: CMC/o /l soap) 3l3 gramsOptical hrightcners 1 gram EXAMPLE X A high foam detergent can beformulated using the softeners of the present invention.

The following ingredients were placed into a mortar:

Softener of Example I 34 grams Sodium carbonate 23 grams L'rea l2 grams(arboxymethylcellulose 4 grams High foam synthetic detergent (2571 -572silicate/471 ethoxvlated fatty alcohol/271 C MC ll /l soap 46 gramsprepared Softener mixture 87 grams High foam synthetic detergent (25%lnear dodecyl benzene sulfonate/ 25% silicate/4'71 ethoxylated fattyalcohol/2% C MC I71 soap 3 13 grams Optical brighteners 1 gram TheN-higher alkyl propylene diamines treated according to the presentinvention can be used to treat a variety of fabrics, which can be madefrom natural animal and vegetable fibers and blends of synthetic fibersas well as entirely from synthetic fibers. These include wool. silk.cotton. linen, glass, acetate, rayon, nylon,,

Dacron, Orlon, blends of Dacron. e.g., with cotton, 0rlon-wool blends.and the like.

Treatment of fabrics with the N-higher alkyl propylene diamines treatedaccording to the present invention is especially advantageous where itis desired to overcome hardness of feel or to enhance softness to touchand minimize fabric yellowing. Advantages realized herewith are softer,fluffier towels. smoother. silkier sheets and pillowcases, longergarment life. and a whiter and/or brighter fabric.

Although the present invention has been described with reference toparticular embodiments and examples, it will be apparent to thoseskilled in the art that variations and modifications of this inventioncan be made and that equivalents can be substituted therefore withoutdeparting from the principles and true spirit of the invention.

What is claimed is:

l. A fabric softening composition comprising 1. N-higheralkyl-1,3-propylene diamine said higher alkyl group having from l222carbon atoms and having been treated by contacting same with a monomerselected from the group consisting of acrylic acid. methacrylic acid,and mixtures thereof. polymerizing the monomer and neutralizing thepolymerized monomer.

2. an additive, said additive selected from the group consisting ofurea. sugar. and mixtures thereof.

2. The fabric softener composition of claim 1 wherein said additive ispresent in amounts ranging from about 1 percent to about 200 percent ofthe total composition by weight.

3. The fabric softener composition of claim 2 wherein said additive isurea.

4. The fabric softener composition of claim 1 wherein said additive isurea.

1. A fabric softening composition comprising
 1. N-higheralkyl-1,3-propylene diamine said higher alkyl group having from 12-22carbon atoms and having been treated by contacting same with a monomerselected from the group consisting of acrylic acid, methacrylic acid,and mixtures thereof, polymerizing the monomer and neutralizing thepolymerized monomer,
 1. A FABRIC SOFTENING COMPOSITION COMPRISING 1.N-HIGHER ALKYL-1,3-PROPYLENE DIAMINE AND HIGHER ALKYL GROUP HAVING FROM12-22 CARBON ATOMS AND HAVING BEEN TREATED BY CONTACTING SAME WITH AMONOMER SELECTED FROM THE GROUP CONSISTING OF ACRYLIC ACID, METHACRYLICACID, AND MIXTURES THEREOF,
 2. AN ADDITIVE, SAID ADDITIVE SELECTED FROMTHE GROUP CONSISTING OF UREA, SUGAR, AND MIXTURES THEREOF.
 2. anadditive, said additive selected from the group consisting of urea,sugar, and mixtures thereof.
 2. The fabric softener composition of claim1 wherein said additive is present in amounts ranging from about 1percent to about 200 percent of the total composition by weight.
 3. Thefabric softener composition of claim 2 wherein said additive is urea.